JP2008143582A - Small bag for liquid, and liquid small bag packaging filled with liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a small bag for liquid and a liquid small bag packaging having excellent gas barrier properties, mechanical strength and tearing properties. <P>SOLUTION: The small bag for liquid comprises a laminated material successively laminating an anchor coat layer of an anchor coat agent and/or an adhesive layer for laminate of an adhesive for laminate, and a heat-sealable resin layer on a coating layer of a laminated film with gas barrier properties composed of a substrate film, a thin film of a vapor-deposited film of carbon-containing silicon oxide, and a coating layer. The small bag for liquid has excellent tearing properties, mechanical strength and gas barrier properties, and its transparency can be ensured. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid sachet and a liquid sachet package, and more specifically, has strength and excellent fastness, excellent barrier properties such as oxygen gas and water vapor, and excellent laminate strength. In addition, liquid sachets that do not impair the flavor and taste of the contents during storage, storage or distribution, and liquids or viscosities of soy sauce, sauces, soup stock, spices, liquors for cooking, etc. The present invention relates to a liquid sachet package formed by filling and packaging various liquid or viscous foods and drinks such as seasonings, soups, fruit juices, and the like composed of body.

  Conventionally, as packaging materials for filling and packaging foods, drinks, chemicals, miscellaneous goods, etc., the content of the contents is blocked, blocked by oxygen gas, water vapor, etc. to prevent alteration, discoloration, etc. Barrier laminates having various forms through which objects can be seen through have been developed and proposed.

  For example, there is a film in which a barrier coat layer is provided on the vapor deposition layer in order to further improve the barrier property (Patent Documents 1 and 2). In Patent Document 1, a primer layer, a vapor deposition thin film layer, a gas barrier film layer, and a seal layer are sequentially laminated on a transparent plastic material. A primer layer is provided to improve adhesion, and examples of the primer layer include a mixture of a polyester resin alone, a polyester resin and one or more mixed resins selected from an isocyanate resin, an epoxy resin, and a melamine resin. Has been. According to the above configuration, it is assumed that transparency and gas barrier properties are excellent, and delamination or the like is not generated in a seal after boiling and retort sterilization.

  In addition, the gas barrier film laminate described in Patent Document 2 is one in which a primer layer, a vapor-deposited thin film layer, a gas barrier coating layer, and an overcoat layer are sequentially laminated on a plastic material. In order to improve adhesion, a primer layer is provided, and examples of the primer layer include acrylic polyols, isocyanate compounds, and silane coupling agents. In Patent Document 2, an adhesive primer layer having excellent heat resistance and dimensional stability is provided on at least one surface of a plastic substrate, and then a vapor-deposited thin film layer / gas barrier film layer is provided as a gas barrier layer, and further excellent in heat resistance. Since it has a protective layer, it has gas barrier properties similar to those of metal foils, and it can suppress deterioration of barrier properties after various sterilization treatments such as boil sterilization and retort sterilization. The overcoat layer is made of a composition containing a styrene / maleic anhydride copolymer, thereby absorbing / relaxing stress from an adhesive portion or a sealant layer by boil / retort treatment, and depositing a thin film layer and a gas barrier property. It is said to protect the coating layer.

  On the other hand, in a gas barrier laminated film having a vapor deposition film, there is also a technique for improving adhesion without providing a primer layer between a substrate and a vapor deposition film layer (Patent Document 3). In Patent Document 3, after a polyethylene terephthalate film provided with a vapor deposition layer made of an inorganic oxide is immersed in treated water and a part of the vapor deposition layer is removed, X-ray photoelectron spectroscopy measurement of the film surface is performed, and C1s A strong adhesion vapor-deposited film having a functional group ratio (COO / C-C) determined from waveform analysis of 0.23 or less is disclosed. When the inorganic oxide is removed by immersion in an aqueous solution to which an amine-based alkali has been added, and the functional group ratio (COO / C-C) is 0.23 or less, the PET film and the inorganic oxide layer are It shows extremely good adhesion.

  Furthermore, there is also a film for retort use comprising a vapor-deposited film of carbon-containing silicon oxide, a gas barrier coating film, an intermediate substrate and a heat-sealable resin layer on a substrate film (Patent Document 4). According to the patent document, a laminate having strength and the like by an intermediate base material and having various properties such as heat resistance, moisture resistance, heat sealability, pinhole resistance, puncture resistance, transparency, and the like. It is said that it is a material.

  Furthermore, as a characteristic requested | required of the packaging material, the tearability at the time of opening is also requested | required besides the intensity | strength in the said retort processing and boil processing. Even if easy opening is ensured by V-notch, U-notch, I-notch, etc., if the film itself is not torn easily, it is not easy to open after the notch, and even if it tears, more force is required than necessary. , Troubles such as not being able to tear in a straight line may occur, and clothes and furniture may be soiled. For this reason, there is also a gas barrier laminated film that ensures tearability as well as gas barrier properties (Patent Document 5). Patent Document 5 discloses a gas barrier easily tearable polyester film in which a gas barrier organic layer is laminated on at least one side of a biaxially stretched film made of a raw material in which a predetermined modified PBT and PET are mixed at a predetermined ratio. The gas barrier organic layer comprises a compound (A) having two or more hydroxyl groups in the molecule and a compound in which at least one carboxyl group is bonded to each of three or more consecutive carbon atoms in the molecule ( B) and the mass ratio (A / B) of A to B is 65/35 to 15/85.

  On the other hand, soy sauce, sauce, soup stock, spices, liquor for cooking, other seasonings consisting of liquid or viscous products, soups, fruit juices, and other various liquid or viscous food and beverage soy sauces, liquids such as sauces In addition to gas barrier properties, liquid sachets filled and packaged with the above-mentioned seasonings are also required to have particularly fastness and chemical resistance and use a polyamide having excellent mechanical strength as a base film. For example, a thickness of 100 is provided on at least one side of a polyamide-based laminated biaxially stretched film including any two layers of three layers of an aromatic polyamide, an aliphatic polyamide, and a mixture of the aromatic polyamide and the aliphatic polyamide. There is a transparent laminated plastic film having an excellent gas barrier property in which a silicon oxide thin film layer is formed in a range of ˜3000 mm (Patent Document 6). Since polyamide is used as the base material, it is said that the gas barrier property and mechanical strength are both excellent, and the barrier property laminate material in which transparency is ensured.

On the other hand, polyamide is excellent in mechanical strength, but may cause troubles in processing steps such as winding failure during vapor deposition and problems of peeling charging. As a technique for improving such winding failure during the deposition of a polyamide film, there is a technique using a biaxially stretched polyamide film having a static friction coefficient of 0.7 or less and a dynamic friction coefficient of 0.6 or less (Patent Document 7). In Patent Document 7, as a means for reducing the friction coefficient of the biaxially stretched polyamide film, a method of adding inorganic particles or organic polymer to polyamide or applying a slipping agent is exemplified, and the dynamic friction coefficient is 0.34 to 0. Manufactures .73 polyamide films.
Japanese Patent Laid-Open No. 10-722 JP 2004-106443 A JP 2005-59265 A JP 2005-178802 A JP 2006-21378 A Japanese Patent Laid-Open No. 6-190961 JP 59-219337 A

  However, the laminated materials described in Patent Documents 1 to 4 do not have sufficient tearability when opened, and the laminated material described in Patent Document 5 does not have sufficient gas barrier properties.

  The film described in Patent Document 6 can reduce oxygen permeability and is advantageous in terms of excellent impact resistance and mechanical strength because polyamide is used as a base film. Due to the hygroscopicity based on this, it is easy to cause a dimensional change. For this reason, when the deposited film cannot follow the expansion and contraction of the polyamide film, cracks and pinholes are generated and it is difficult to maintain the barrier performance. In particular, the friction coefficient and the transparency of the film have a trade-off relationship, and as in Patent Document 7, when inorganic particles or organic polymer particles are added to lower the dynamic friction coefficient, the transparency of the film is ensured. It becomes difficult. In addition, when the irregularities on the film surface become large due to the addition of these particles, gaps between the vapor deposition layers are likely to occur, and the gas barrier properties are lowered.

  In addition, liquid sachets contain various contents, so that depending on the contents, the sachets may be broken by the shape of the contents during filling or transportation, or pinholes may be generated, preserving the contents. May be.

  Therefore, the present invention provides a liquid sachet and a liquid sachet package that have excellent mechanical strength, barrier properties that prevent permeation of oxygen gas, water vapor, and the like, transparency is ensured, and excellent laminate strength. Objective.

  As a result of detailed examination of the gas barrier laminated film constituting the liquid pouch, the inventor has a coefficient of dynamic friction of 0.4 or less, a haze of 6.0% or less, and an ash test performance of 15 mm or less. When a biaxially stretched polyamide film having a surface roughness of 2000 nm or less is used as a base film, slipperiness is improved and static electricity troubles are prevented, so that troubles occurring in the subsequent process of the filling machine can be avoided. When a vapor deposition film of carbon-containing silicon oxide is formed on the surface of the polyamide film having a surface roughness of 2000 nm or less by vapor deposition of organic-containing silicon oxide or the like by chemical vapor deposition, a flexible film is formed on the base film. A vapor-deposited film of high carbon-containing silicon oxide can be formed. Further, a predetermined polyurethane resin composition is formed on the vapor-deposited thin film. If the coating film is provided, adhesion to the heat seal layer can be secured, delamination can be prevented by ensuring the above adhesion and flexibility, and tearing of the gas barrier laminate film can be achieved by avoiding delamination. As a result, the present inventors have found that the use of the gas barrier laminate film results in a liquid sachet having excellent mechanical strength such as puncture resistance and pinhole resistance during transportation.

  The liquid sachet of the present invention uses a biaxially stretched polyamide film having a dynamic friction coefficient of 0.4 or less at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10% as a base film, thereby providing gas barrier properties and transparency. Excellent.

  In addition, since the liquid sachet of the present invention uses a gas barrier laminated film in which an organic-containing silicon oxide oxide is deposited by plasma chemical vapor deposition, the base film and the organic-containing silicon oxide oxide have gas barrier properties. Adhesion can be ensured, and flexibility such as spreadability, flexibility, and flexibility can be imparted to the vapor deposition layer.

  Since the gas barrier laminate film used for the liquid pouch according to the present invention has a coating layer made of a polyurethane resin composition containing a silane coupling agent and a filler on the vapor-deposited layer of the organic-containing silicon oxide, The strength is further improved and the resistance to sticking is particularly excellent.

  Further, coupled with the improvement of the adhesion strength, the liquid sachet of the present invention is excellent in tearability.

The first aspect of the present invention is that the gas barrier laminate film composed of a base film and an inorganic oxide vapor-deposited film and a coating thin film is laminated on the coating thin film using an anchor coating layer and / or a laminating adhesive. A liquid sachet made of a laminated material obtained by sequentially laminating an adhesive layer for heat and a heat-sealable resin layer,
The gas barrier laminate film has a biaxial structure in which the base film has a dynamic friction coefficient of 0.4 or less, a haze of 6.0% or less, an ash test performance of 15 mm or less, and a surface roughness of at least one surface of 2000 nm or less. It is a stretched polyamide film, and an inorganic oxide vapor deposition film is provided on the surface of the base film having a surface roughness of 2000 nm or less, and a silane coupling agent and a filler are included on the surface of the inorganic oxide vapor deposition film. A coating thin film made of a polyurethane resin composition is provided,
The liquid sachet is a liquid in which the laminated material is overlapped with the heat-sealable resin layer facing each other to heat-seal the outer periphery and provide a heat-seal portion to form a bag body. It is a small bag. Hereinafter, the present invention will be described in detail.

(1) Gas barrier laminate film and laminate As shown in FIG. 1 (a), the gas barrier laminate film used in the present invention comprises a base film (10), an inorganic oxide vapor deposition film (20) and a coating thin film. (30). Furthermore, as shown in FIG.1 (b), you may have a surface treatment layer (10 ') and (20') on a base film (10) and a vapor deposition film (20), respectively. Moreover, as shown in FIG.1 (c), you may have a printing layer (50) on the coating thin film (30) further. In addition, the laminated material used in the present invention includes, for example, a coating thin film (30) of the gas barrier laminate film shown in FIG. 1 (b), an anchor coat layer formed of an anchor coat agent and / or an anchor coat agent as shown in FIG. 1 (d). Alternatively, a laminating adhesive layer (60) by a laminating adhesive and a heat-sealable resin layer (70) are sequentially laminated. For example, in the coating thin film (30) of the gas barrier laminate film shown in FIG. 1 (c), as shown in FIG. 1 (e), the anchor coating layer by the anchor coating agent and / or the laminating adhesive layer by the laminating adhesive is used. (60) and a heat-sealable resin layer (70) may be laminated in sequence. The print layer (50) may be full-surface printing or partial printing.

(2) Base film In the present invention, a polyamide film is used as the base film. The base film used in the present invention has excellent chemical or physical strength, can withstand the conditions for forming an inorganic oxide vapor-deposited film, and impairs the film characteristics of the inorganic oxide vapor-deposited film. And a polyamide film that can be held well and has a dynamic friction coefficient of 0.4 or less, more preferably 0.3 or less, and a haze of 6.0% at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10%. Or less, more preferably 4.0% or less, ash test performance is 15 mm or less, more preferably 8 to 12 mm, and at least one surface has a surface roughness of 2000 nm or less, more preferably 1500 nm, a biaxially stretched polyamide film. It is.

  The present invention uses a biaxially stretched polyamide film that is excellent in mechanical strength because it aims at a gas barrier laminate film having high durability, but the polyamide film easily absorbs moisture and is inferior in slipperiness. On the other hand, it is difficult to ensure both slipperiness and gas barrier properties, and if inorganic particles are blended to ensure slipperiness, it will not make sense to deposit an inorganic oxide vapor deposition film to ensure gas barrier properties. In some cases, transparency is also reduced. Therefore, in the present invention, a gas barrier laminate film having excellent gas slidability and transparency, preventing wrinkles during winding, having excellent roll winding appearance, and improving laminate adhesive strength and having high gas barrier properties. In order to produce a base film, the dynamic friction coefficient at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10% is 0.4 or less, the haze is 6.0% or less, and the ash test performance is 15 mm or less, It was limited to a biaxially stretched polyamide film having a surface roughness of at least 2000 nm on one surface.

  Such a polyamide film may be an aliphatic polyamide, an aromatic polyamide, or a composition in which these are mixed. Specific examples of preferred polyamides include polycaproamide (nylon 6), poly-ε-aminoheptanoic acid (nylon 7), poly-ε-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin Lactam (nylon 12), polyethylenediamine adipamide (nylon 2.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene adipamide (nylon 6/6), polyhexamethylene sebacamide (Nylon 6 · 10), Polyhexamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene adipamide (Nylon 8.6), Polydecamethylene adipamide (Nylon 10/6), polydecamethylene sebacamide (nylon 10/10), Polydodecamethylene dodecamide (nylon 12 and 12), metaxylenediamine-6 nylon (MXD6) and the like may be used, and a copolymer containing these as main components may be used. Examples thereof include caprolactam / Laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer And ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, and the like. It is also effective to blend these polyamides with plasticizers such as aromatic sulfonamides, p-hydroxybenzoic acid, esters, elastomer components with low elastic modulus, and lactams as film flexibility modifiers. is there. The polyamide film is a conventionally known polyamide film having a haze of 6.0% or less and a dynamic friction coefficient of 0.4 or less. The ash test performance is 15 mm or less, and the surface roughness of at least one surface is at least. The thing below 2000 nm can be selected and used.

  In the present invention, the film thickness of the substrate film is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.

  When forming the polyamide film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, mold release properties, flame retardancy, antifungal properties, strength, etc. Various plastic compounding agents, additives, etc. can be added for the purpose of improving and modifying the contents, etc., and the addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. can do.

  In the above, as a general additive, for example, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. In this case, a modifying resin or the like can also be used.

(3) Surface treatment In this invention, although the vapor deposition film | membrane of an inorganic oxide is formed in one surface of said base film, you may surface-treat a base film previously. Thereby, the adhesiveness between the base film and the vapor-deposited film of the inorganic oxide can be improved.

  Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there.

  In addition, a primer coating agent, an undercoat agent, an anchor coating agent, a vapor deposition anchor coating agent, or the like can be arbitrarily applied to the surface of the base film used in the present invention in advance for surface treatment. Examples of the coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyolefins such as polyethylene or polypropylene. A resin composition containing a resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  Among such surface treatments, it is particularly preferable to perform corona treatment or plasma treatment. For example, as plasma processing, there is plasma processing in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. In addition to the above, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas can be used as the plasma gas. For example, immediately before forming a vapor-deposited film of an inorganic oxide by chemical vapor deposition, which will be described later, in-line plasma treatment removes moisture and dust from the surface of the base film and smoothes the surface. Surface treatment such as activation, etc. can be made possible. In addition, after the vapor deposition, plasma treatment can be performed to improve the adhesion between the vapor deposition layer and another layer stacked thereon. Note that the plasma discharge treatment is preferably performed in consideration of the plasma output, the type of plasma gas, the supply amount of the plasma gas, the treatment time, and other conditions. Moreover, as a method for generating plasma, DC glow discharge, high frequency discharge, microwave discharge, and other devices can be used. In addition, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

(4) Inorganic oxide vapor-deposited film As the inorganic oxide vapor-deposited film, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination of these is used to form a single layer of an inorganic oxide vapor-deposited film. It can be produced by forming a layer film or a multilayer film or a composite film composed of two or more layers.

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. As described above, a vapor deposition film of an inorganic oxide such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like and using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

  An example of the formation method of the vapor deposition film | membrane of an inorganic oxide by said low temperature plasma chemical vapor deposition method is demonstrated using FIG. 2 which is a schematic block diagram of a low temperature plasma chemical vapor deposition apparatus.

  In the present invention, the base film 201 is fed out from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the base film 201 is further fed at a predetermined speed via the auxiliary roll 224. Then, it is conveyed onto the circumferential surface of the cooling / electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The vapor deposition mixed gas composition is supplied onto the substrate film 201 transported on the circumferential surface of the cooling / electrode drum 225, and is generated and irradiated with glow discharge plasma 230 to generate an inorganic oxide such as silicon oxide. The deposited film is formed. Next, if the base film 201 on which the inorganic oxide vapor deposition film such as silicon oxide is formed is wound on the take-up roll 234 via the auxiliary roll 233, the inorganic oxide vapor deposition film by the plasma chemical vapor deposition method is used. Can be formed. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. This glow discharge plasma is derived from one or more gas components in the mixed gas. When the substrate film is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum surface to be A deposited film of an inorganic oxide such as silicon oxide can be formed on the base film. In FIG. 2, reference numeral 235 represents a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr is preferable, and the conveying speed of the base film is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of a vapor-deposited film of an inorganic oxide such as silicon oxide obtained in this way is formed on a base film in the form of a thin film in the form of SiO _x while oxidizing the plasma source gas with oxygen gas. Therefore, the deposited film of inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is flexible. Accordingly, the barrier property of the deposited film of inorganic oxide such as silicon oxide is It is much higher than a vapor deposition film of an inorganic oxide such as silicon oxide formed by a conventional vacuum vapor deposition method, and a sufficient barrier property can be obtained with a thin film thickness. Moreover, since the surface of the base film is cleaned by SiO _x plasma, and polar groups, free radicals, etc. are generated on the surface of the base film, the deposited film of inorganic oxide such as silicon oxide and the base material are formed. The tight adhesion with the film is high. Further, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the vacuum degree when forming a deposited film of an inorganic oxide such as silicon oxide by the conventional vacuum deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the vacuum state setting time at the time of replacing the raw material film, and the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is It is closely bonded to one surface of a base film to form a dense thin film having high flexibility, and is usually represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon oxide. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the silicon oxide vapor deposition film can be varied by changing the conditions of the vapor deposition process. In this case, the content of the above-mentioned compound in the deposited film of silicon oxide is 0.1 to 50% by mass, preferably 5 to 20% by mass. When the content is less than 0.1% by mass, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film are insufficient, and scratches, cracks, etc. are likely to occur due to bending, etc., and high barrier properties. May be difficult to maintain stably, and on the other hand, if it exceeds 50% by mass, the barrier property may be lowered.

  Further, in the present invention, in the silicon oxide vapor-deposited film, it is preferable that the content of the above compound decreases in the depth direction from the surface of the silicon oxide vapor-deposited film. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, since the content of the above compound is small at the interface with the base film, the vapor deposition of the base film and the silicon oxide is performed. The tight adhesion with the film becomes strong.

  In the present invention, the above-described vapor deposition film of silicon oxide uses, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above-mentioned physical properties can be confirmed by performing analysis such as ion etching in the vertical direction and performing elemental analysis of the deposited film of silicon oxide.

  In the present invention, the thickness of the silicon oxide vapor-deposited film is preferably about 50 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 50 mm, it may be difficult to achieve a barrier effect. The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. As a means for changing the film thickness of the silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. be able to.

  In the present invention, the inorganic oxide vapor-deposited film may be not only one layer of the inorganic oxide vapor-deposited film but also a multilayer film in which two or more layers are laminated, and one or two materials are used. It is also possible to form a vapor-deposited film of an inorganic oxide that is used as a mixture of seeds or more and mixed with different materials.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyl Trimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane , Methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

  On the other hand, in the present invention, an inorganic oxide vapor-deposited film can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an inorganic oxide can be formed by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. A vapor deposition film can be formed.

  Specifically, a metal or metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the base films, or a metal or metal oxide as a raw material. Used to oxidize by introducing oxygen and oxidize and deposit on one side of the base film, and further use plasma-assisted oxidation reaction deposition method that promotes oxidation reaction with plasma to form a deposited film can do. In addition, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. A method of forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 3 showing a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.

  First, the base film 201 fed out from the unwinding roll 243 is guided to the cooled coating drum 246 through the guide rolls 244 and 245 in the vacuum chamber 242 of the wind-up type vacuum evaporation apparatus 241. The evaporation source 248 heated by the crucible 247, for example, metal aluminum or aluminum oxide is evaporated on the substrate film 201 guided on the cooled coating drum 246, and if necessary, While an oxygen gas or the like is ejected from the oxygen gas outlet 249 and supplied, an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 250 and 250. When the base film 201 on which an inorganic oxide vapor deposition film such as aluminum oxide is formed is sent out through the guide rolls 251 and 252 and wound around the take-up roll 253, the inorganic oxide vapor deposition film is formed by physical vapor deposition. Can be formed. In addition, using the above-described winding-type vacuum vapor deposition apparatus, first, a first-layer inorganic oxide vapor-deposited film is formed, and then an inorganic oxide vapor-deposited film is further formed thereon, or A vacuum evaporation apparatus may be connected in series, and an inorganic oxide vapor deposition film may be continuously formed to form an inorganic oxide vapor deposition film composed of a multilayer film of two or more layers.

The vapor deposition film of metal or inorganic oxide may basically be a thin film on which a metal oxide is deposited, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca). , Vapor deposition films of metal oxides such as potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) Can be used. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. In the present invention, silicon or aluminum is preferable as M. In this case, the value of X is 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). . In addition, although the film thickness of the vapor deposition film | membrane of an inorganic oxide changes with kinds etc. of the metal to be used or a metal oxide, it can select arbitrarily within the range of 50-2000 mm, for example, Preferably, it is 100-1000 mm. it can. In addition, as the inorganic oxide vapor deposition film, the metal or metal oxide to be used is used in one kind or a mixture of two or more kinds to constitute a vapor deposition film of an inorganic oxide mixed with different materials. You can also.

  Further, in the present invention, for example, a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition.

  As a composite film composed of two or more layers of the above-mentioned different kinds of inorganic oxide vapor-deposited films, first, a chemical vapor deposition method is used on a base film, and it is dense and flexible, and relatively cracks are generated. An inorganic oxide vapor-deposited film that can prevent the formation of an inorganic oxide, and then an inorganic oxide vapor-deposited film formed by physical vapor deposition on the inorganic oxide vapor-deposited film. It is preferable to constitute an inorganic oxide vapor deposition film. Contrary to the above, on the base film, first, a vapor deposition film of an inorganic oxide is provided by a physical vapor deposition method, and then dense and flexible by a chemical vapor deposition method. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film that can relatively prevent the occurrence of cracks.

(5) Coating thin film The coating thin film by the polyurethane-based resin composition of the present invention is made of a polyurethane-based resin composition containing a silane coupling agent and a filler, and the coating thin film is a vapor-deposited film of the inorganic oxide or a surface thereof. It is formed on the treatment layer.

  As the silane coupling agent used for the coating thin film, organic functional silane monomers having binary reactivity can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane. , Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ -Mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β -Hide Kishiechiru)-.gamma.-aminopropyltriethoxysilane, .gamma.-aminopropyl silicone - can be used one or more of the aqueous solution or the like of the emission.

  In the silane coupling agent as described above, a functional group at one end of the molecule, usually chloro, alkoxy, or acetoxy group is hydrolyzed to form a silanol group (SiOH), which is the barrier coating. Silane coupling occurs on the barrier coating film by causing a reaction such as a reaction such as dehydration condensation reaction with silicon contained in the film or an active group on the barrier coating film, for example, a functional group such as a hydroxyl group. The agent is modified with a covalent bond or the like, and further, a strong bond is formed by adsorption of the silanol group itself onto the barrier coating film or hydrogen bond. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto on the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. For example, an adhesive layer for laminating It reacts with substances constituting the anchor coat layer and other layers to form a strong bond. As a result, in the present invention, the barrier coating film and the heat-sealable resin layer are firmly and closely bonded via the adhesive bond layer, the anchor coat layer, and the like by the chemical bond as described above. Strength can be increased and a strong laminated structure with high laminate strength can be formed. In particular, in the present invention, a monomer for vapor deposition of an organic silicon compound is used to form a vapor-deposited film of carbon-containing silicon oxide, but an organic silicon compound such as tetraethoxysilane used for the formation of the vapor-deposited film is formed on the coating thin film. It is considered that each thin film is firmly bonded by the common components. In particular, adhesion with an anchor coat layer is ensured by laminating a coating layer containing a silane coupling agent, and thus adhesion with a heat seal layer laminated on these is also ensured, such as laminate strength. Will improve.

  As the filler, for example, calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like can be used. This is to improve the coating suitability and the like of the polyurethane resin composition by adjusting the viscosity and the like.

  Specific examples of the polyurethane-based resin include a polymer obtained by reaction of a polyfunctional isocyanate and a hydroxyl group-containing compound, specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene. Polyfunctional isocyanates such as aromatic polyisocyanates such as polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate, and polyether polyols, polyester polyols, polyacrylate polyols, etc. One-pack or two-pack polyurethane resins obtained by reaction with a hydroxyl group-containing compound can be used. Thus, in the present invention, by using the polyurethane-based resin as described above, the degree of elongation of the coating thin film is improved, and the post-processing suitability such as laminating or bag making is improved. It prevents the occurrence of cracks in the thin film of inorganic oxide during processing.

  As said polyurethane-type resin composition, a silane coupling agent, about 0.05-10 mass% with respect to a polyurethane-type resin, 1-30 mass%, Preferably, about 0.1-5 mass%, a filler Add about 0.1 to 20% by mass, preferably about 1 to 10% by mass, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. Is added arbitrarily, a solvent, a diluent, etc. are added and mixed well to prepare a polyurethane resin composition. Thus, in the present invention, the polyurethane resin composition as described above is applied onto the inorganic oxide thin film by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods. After coating, the coating film is dried to remove the solvent, diluent, etc., and the gas barrier laminate film according to the present invention can be formed. In addition, in this invention, as a film thickness of the coating thin film by a polyurethane-type resin composition, about 0.01-50 micrometers, for example, Preferably, about 0.1-5 micrometers is desirable.

(6) Laminating adhesive In the present invention, a base film such as a heat seal layer can be laminated on the surface of the coating layer via a laminating adhesive using a dry laminating method. In addition, when any two layers are laminated, they can be adhered by a dry laminate lamination method via a laminating adhesive.

  The adhesive for laminating comprises a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Polyacrylate adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives Polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive type (meta ) Acrylic acid adhesive, chloroprene rubber, nitrile Beam, styrene - inorganic adhesive made of butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of low-melting glass, it is possible to use other adhesives.

  More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide It can act and improve processing aptitude, such as lamination processing and printing processing, and can avoid generation of a crack etc. to a barrier thin film layer which consists of inorganic oxides. The laminate adhesive layer made of the above-mentioned laminate adhesive preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

  The composition system of these adhesives may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like.

Although there is no limitation in the usage-amount of the adhesive agent for lamination, Generally, it is 0.1-10 g / m < ² > (dry state). The laminating adhesive can be applied by roll coating, gravure coating, kiss coating or other coating methods or printing methods.

(7) Printed layer In the present invention, a desired printed pattern layer can be formed on any of the layers forming the gas barrier laminate film or a substrate layer described later. As the printed pattern layer, for example, a normal gravure ink composition, an offset ink composition, a letterpress ink composition, a screen ink composition, and other ink compositions are used on the coating layer, for example, , Gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods, for example, by forming a desired printing pattern consisting of characters, figures, patterns, symbols, etc. be able to.

  Regarding the ink composition, examples of the vehicle constituting the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, and polyvinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin Resins, polyamide resins, alkyd resins, epoxy resins, unsaturated polyester resins, thermosetting poly (meth) acrylic resins, melamine resins, urea resins, polyurethane resins, phenol resins, xylene resins , Maleic resin, Fiber resins such as rocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, natural resins such as petroleum resins, rosin and casein, linseed oil, soybean oil, etc. A mixture of one or more of fats and oils and other resins can be used. In the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of coloring agents such as dyes and pigments are added to this, and if necessary, a filler, Light stabilizers such as additives, plasticizers, antioxidants, UV absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, solvent, dilution Ink compositions having various forms obtained by sufficiently kneading with an agent or the like can be used.

  The print layer may be printed by surface printing or reverse printing of a desired printing pattern such as a character, a figure, a symbol, a pattern, or a pattern, and may be full surface printing or partial printing.

(8) Anchor coat layer In the present invention, a heat seal can be laminated on the coating layer by extrusion. When the heat seal layer is formed by extrusion, the heat seal layer is preferably formed on the coating layer via an anchor coat agent. Examples of the anchor coating agent to be used include isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, and other anchor coating agents. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide Acting, improving processability such as laminating and printing, avoiding the occurrence of cracks in the barrier thin film layer made of inorganic oxide, and tight adhesion between the gas barrier laminate film and the heat seal layer It is possible to improve the property, prevent the occurrence of cracks in the barrier thin film layer made of an inorganic oxide, and improve the laminate strength.

In the present invention, the anchor coating agent is coated by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and the solvent, diluent or the like is dried, and the anchor according to the present invention is applied. An anchor coat layer with a coating agent can be formed. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). The anchor coat layer made of the anchor coat agent preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

(9) Heat-seal layer As the heat-seal layer, polyolefin resins having various heat-seal properties that can be melted by heat and fused to each other can be used. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resins, poly (meth) acrylic resin, one or more films made of a resin such as polyvinyl chloride resin or sheet or coated film and the like can be used.

  The heat seal layer may be a single layer or a multilayer composed of one of the above resins, and the thickness of the heat seal layer is 15 to 130 μm. If the thickness is less than 15 μm, scratches and cracks may occur in the deposited film of carbon-containing silicon oxide.

(10) Substrate Layer The liquid sachet of the present invention may further have a substrate layer laminated on the other surface of the substrate film. The base material layer is a basic material of the liquid sachet, and is excellent in mechanical, physical, and chemical properties. In particular, the base material layer is a resin film or sheet having strength and toughness and heat resistance. Specifically, for example, tough materials such as polyester resins, polyamide resins, polyaramid resins, polyolefin resins, polycarbonate resins, polystyrene resins, polyacetal resins, fluorine resins, etc. Resin films or sheets, and the like can be used. As the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm. The base material layer may be subjected to surface printing or back printing by a normal printing method with a desired printing pattern such as characters, figures, symbols, patterns, and patterns.

As a base material layer, the various paper base materials which comprise a paper layer may be sufficient, for example. As a paper base material, it has formability, bending resistance, rigidity, etc., for example, a paper base material with high sizing property or unbleached paper, or pure white roll paper, kraft paper, paperboard, processed paper Paper base materials such as, etc., etc. can be used. In the above, as the paper substrate constituting the paper layer, it is desirable to use a material having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² . You may use together the paper base material which comprises a paper layer, and the film | membrane thru | or sheet | seat of various resin as the base material layer mentioned above.

  In addition, since liquid sachets are subjected to severe physical and chemical conditions, the laminated materials constituting liquid sachets are required to have strict packaging suitability, deformation prevention strength, drop impact strength, Various conditions such as pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, and hygiene are required. A material that satisfies the above various conditions can be arbitrarily selected and used as the base material layer. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate. Copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, Poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin Resin, Polycar From films or sheets of known resins such as nate resins, polyvinyl alcohol resins, saponified ethylene-vinyl acetate copolymers, fluorine resins, diene resins, polyacetal resins, polyurethane resins, nitrocellulose, etc. It can be arbitrarily selected and used. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used. In the present invention, the film or sheet may be any of unstretched, uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm. Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

(11) Liquid sachet The liquid sachet of the present invention is provided with an inorganic oxide vapor-deposited film (20) on one surface of the base film (10) in advance, and further on the surface of the vapor-deposited film (20). Further, an anchor coat layer by an anchor coat agent and / or a laminate adhesive layer by a laminate adhesive and a heat sealable resin layer are formed on the coating layer of the gas barrier laminate film obtained by laminating a coating layer (40). This is a liquid sachet made of laminated materials sequentially laminated.

  As a method for producing a laminated material, a method for laminating a normal packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, etc. Method, coextrusion inflation method, etc. Thus, in the present invention, when the above lamination is performed, surface treatment such as corona treatment or ozone treatment can be performed as necessary as described above.

  In the present invention, a pouch for liquid can be produced using the laminated material. For example, the surface of the heat sealable film of the inner layer of the laminated material is made to face and be folded, or two of them are overlapped, and the peripheral end portion is further heat sealed to provide a seal portion to form a bag body Can be configured. As the bag making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side seal type, two-side seal Heat seal by heat seal form such as mold, three-side seal type, four-side seal type, envelope sticker seal type, palm seal sticker type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. Various types of liquid sachets according to the present invention can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) can be manufactured.

  In the above, the heat sealing method can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, and the like. In the present invention, for example, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the liquid pouch as described above. In addition, the shape can be any of a rectangular container, a cylindrical shape such as a round shape, and the like.

(12) Liquid sachet packaging body The liquid sachet packaging body of the present invention is a liquid sachet, soy sauce, sauce, soup stock, spice, cooking liquor, etc. Filled and packaged with various liquid or viscous foods such as fruit juices and others. The contents can be used for filling and packaging various articles such as chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, etc., in addition to the above-mentioned food and drink.

  The liquid sachet package of the present invention is molded using the above laminated material, and the laminated material is a polyamide having excellent mechanical strength such as sticking resistance, and a carbon-containing silicon oxide vapor-deposited film. By laminating a thin film, gas barrier properties and flexibility are ensured, and further, by laminating a coating layer, gas barrier properties and laminate strength are ensured, so the obtained liquid sachet package has excellent storage stability of the contents, In addition, it is robust against pointing and pinholes that occur during transportation, and it is unlikely to damage the flavor and taste of the contents during storage, storage or distribution.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.

Example 1
(1) On the one hand, a biaxially stretched polyamide film having a corona-treated surface and having a thickness of 15 μm (dynamic friction coefficient 0.3, haze 3.2%, ash test performance 12 mm, surface roughness 1500 nm) is used. The plasma chemical vapor deposition apparatus shown in FIG. Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.

  On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device and mixed with oxygen gas and inert gas helium supplied from the gas supply device. The raw material gas was used.

As the raw material gas used in the film forming chamber, the mixing ratio of the raw material gas is HMDSO: O ₂ : He: Ar = 1.2: 6.0: 0.5: 0.5 (unit: slm, standard liter minute) ), Film forming output: 10 kW, and then transporting the 12 μm-thick biaxially stretched polyamide film at a line speed of 200 m / min on the corona-treated surface of the 12 μm-thick biaxially stretched polyamide film. A deposited silicon oxide film having a thickness of 15 nm was formed.

Next, a glow discharge plasma generator is used on the surface of the inorganic oxide vapor deposition film, and the power is 9 kw, and oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm). Using a mixed gas, oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a treatment speed of 420 m / min to improve the surface tension of the deposited surface of the inorganic oxide by 54 dyne / cm or more. Thus, a gas treated barrier film 1 was produced by forming a plasma treated surface.

  (2) Using γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, 1.2% by mass of the silane coupling agent, 1.0% by mass of silica powder, 13-15% by mass of polyurethane resin, A polyurethane resin composition comprising 31 to 32% by mass of toluene, 29 to 30% by mass of methyl ethyl ketone (MEK), and 15 to 16% by mass of isopropyl alcohol (IPA) was prepared.

Next, the above-mentioned polyurethane resin composition is used to coat the vapor-deposited film of the above (2) using a gravure roll coating method, and then dried at 100 ° C. for 5 seconds. A coating layer (thickness 0.3 g / m ² , dry state) was formed from the resin composition.

(3) On the coating layer, a polyurethane-based anchor coating agent was coated in the same manner as described above to form an anchor coat layer having a thickness of 0.2 g / m ² (dry state).

  (4) Furthermore, on the anchor coat layer, an ethylene / α-olefin copolymer (LDPE, MI = 8.0, density = 0.911) polymerized using a Ziegler catalyst is melt extruded. At that time, an extrusion process was performed while applying ozone treatment to the melt-extruded resin surface to form an adhesive layer having a thickness of 20 μm. Next, 80% by weight of an ethylene / α-olefin copolymer (LLDPE, MI = 7.3, density = 0.900) polymerized with a single-site catalyst on the above adhesive layer and ethylene / butene copolymer. A blend comprising 20% by weight of a polymer (MI = 3.5, density = 0.855, butene content 20%) was melt extrusion coated at an extrusion temperature of 290 ° C. and a processing speed of 100 m / min to obtain a thickness. A laminate 1 was produced by forming a 20 μm heat-sealable resin layer.

Example 2
An anchor coat layer was formed in the same manner as in Example 1 (1) to (3).

  Next, an ethylene / α-olefin copolymer (LDPE, MI = 8.0, density = 0.911) polymerized using a Ziegler catalyst is melt-extruded onto the anchor coat layer, Extrusion was performed by an extrusion method while applying ozone treatment to the extruded resin surface to form an adhesive layer having a thickness of 20 μm. Next, on this adhesive layer, 80% by mass of ethylene / α-olefin copolymer (LLDPE, MI = 7.3, density = 0.900) polymerized by a single site catalyst and ethylene / butene copolymer A 20 μm thick heat-sealable resin film obtained by forming a blend of 20% by mass (MI = 3.5, density = 0.855, butene content 20%) using an inflation method is laminated. And the laminated material 2 was manufactured.

Comparative Example 1
In Example 1, a biaxially stretched polyamide film having a thickness of 15 μm was used instead of the biaxially stretched polyamide film having a thickness of 15 μm (dynamic friction coefficient 0.3, haze 2.4%, ash test performance 12 mm, surface roughness 1500 nm). Comparative laminate 1 was prepared in the same manner as in Example 1 except that (dynamic friction coefficient 0.6, haze 2.4%, ash test performance 12 mm, surface roughness 1500 nm) was used.

Comparative Example 2
A comparative laminate 2 was prepared in the same manner as in Example 1 except that the coating layer formed of the polyurethane resin composition described in (3) of Example 1 was not provided.

Evaluation method The laminate materials manufactured in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were subjected to a laminate strength test and a heat seal strength test. The results are shown in Table 1 below.

(I) Laminate strength test:
Using a peeling tester (Orientec Co., Ltd., model name, Tensilon universal testing machine), sample 15 mm width, peeling angle 90 degrees, peeling speed 50 mm / min, distance between fulcrums 50 mm, peeling method T-shaped peeling conditions The laminate strength test was conducted.

(Ii) Heat seal strength:
Sealing conditions: 140 ° C. × 1 kg / cm ² × 1 second, using the above peeling tester, heat seal under the conditions of sample 15 mm width, peeling speed, 300 mm / min, distance between fulcrums, 50 mm, T-shaped peeling A strength test was performed.

ＩＩ．
実施例１、実施例２、比較例１、比較例２で製造した積層材および該積層材で構成した液体用小袋について、印刷、貼り合せ、スリット、充填工程でのトラブルについて観察を実施した。結果を下記の表２に示す。

II.
With respect to the laminated materials produced in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 and the liquid sachet composed of the laminated materials, the printing, bonding, slitting, and troubles in the filling process were observed. The results are shown in Table 2 below.

  The liquid sachet according to the present invention is particularly useful because it is excellent in mechanical strength, gas barrier properties, laminate strength, transparency, and is excellent in the preservation of contents.

Fig.1 (a)-(e) is a cross-sectional view explaining the gas gas barrier laminated film of this invention. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus.

Explanation of symbols

10 ... base film,
10 '... plasma surface treatment surface 20 ... deposited film of inorganic oxide,
20 '... corona surface treatment surface,
30 ... coating thin film,
50 ... printing layer,
60 ... Laminate adhesive layer,
70: Heat seal layer.

Claims (8)

On the coating thin film of the gas barrier laminate film comprising a base film and an inorganic oxide vapor deposition film and a coating thin film, an anchor coating layer by an anchor coating agent and / or a laminating adhesive layer by a laminating adhesive, and heat sealability A liquid sachet made of a laminated material in which resin layers are sequentially laminated,
The gas barrier laminate film has a biaxial structure in which the base film has a dynamic friction coefficient of 0.4 or less, a haze of 6.0% or less, an ash test performance of 15 mm or less, and a surface roughness of at least one surface of 2000 nm or less. It is a stretched polyamide film, the surface roughness of the base film is 2000 nm or less, an inorganic oxide vapor-deposited film is provided, and the inorganic oxide vapor-deposited film includes a silane coupling agent and a filler. A coating thin film made of a polyurethane resin composition is provided,
The liquid sachet is a liquid in which the laminated material is overlapped with the heat-sealable resin layer facing each other to heat-seal the outer periphery and provide a heat-seal portion to form a bag body. Sachets.   The liquid pouch according to claim 1, wherein a base material layer is further laminated on the other surface of the base film.   The liquid sachet according to claim 1 or 2, wherein the inorganic oxide vapor deposition film is an inorganic oxide vapor deposition film such as silicon oxide or an inorganic oxide vapor deposition film such as aluminum oxide.   4. The liquid sachet according to claim 1, wherein the inorganic oxide thin film is an inorganic oxide vapor-deposited film formed by a chemical vapor deposition method.   The anchor coat layer by the anchor coat agent and / or the adhesive layer for laminating by the laminating adhesive has a tensile elongation of 100 to 300% based on JIS standard K7113. The liquid pouch according to any one of claims 1 to 4.   The liquid pouch according to any one of claims 1 to 5, wherein a printing layer is laminated on the base material layer, an inorganic oxide vapor deposition film, the coating thin film, or a surface treatment layer thereof.   The liquid sachet according to any one of claims 1 to 6, wherein the filler comprises silica particles.   A liquid sachet package comprising the liquid sachet according to any one of claims 1 to 7 filled and packaged with a liquid or a viscous material from an opening thereof.

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